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A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes

Das, Biswanath LU ; Al-Hunaiti, Afnan ; Carey, Akina ; Lidin, Sven LU ; Demeshko, Serhiy ; Repo, Timo and Nordlander, Ebbe LU (2022) In Journal of Inorganic Biochemistry 231.
Abstract

The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in... (More)

The oxido-bridged diiron(III) complex [Fe2(μ-O)(μ-OAc)(DPEAMP)2](OCH3) (1), based on a new unsymmetrical ligand with an N4O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H2O2 as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H2O2 and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)2-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.

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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Catalysis, Epoxidation, Hydroxylation, Iron, Metal-oxido complex, Peroxide complex
in
Journal of Inorganic Biochemistry
volume
231
article number
111769
publisher
Elsevier
external identifiers
  • scopus:85126777903
  • pmid:35287038
ISSN
0162-0134
DOI
10.1016/j.jinorgbio.2022.111769
language
English
LU publication?
yes
id
bc446e1b-d993-4bba-9eb9-7ff0864fbd3d
date added to LUP
2022-04-19 12:41:02
date last changed
2024-06-15 18:41:12
@article{bc446e1b-d993-4bba-9eb9-7ff0864fbd3d,
  abstract     = {{<p>The oxido-bridged diiron(III) complex [Fe<sub>2</sub>(μ-O)(μ-OAc)(DPEAMP)<sub>2</sub>](OCH<sub>3</sub>) (1), based on a new unsymmetrical ligand with an N<sub>4</sub>O donor set, viz. [2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-((ethylamino)methyl)-4-methylphenol (HDPEAMP)], has been prepared and characterized by spectroscopic methods and X-ray crystallography. The crystal structure of the complex reveals that each Fe(III) ion is coordinated by three nitrogen and three oxygen donors, two of which are the bridging oxido and acetate ligands. Employing H<sub>2</sub>O<sub>2</sub> as a terminal oxidant, 1 is capable of oxidizing a number of alkanes and alkenes with high activity. The catalytic oxidation of 1,2-dimethylcyclohexane results in excellent retention of configuration. Monitoring of the reaction of 1 with H<sub>2</sub>O<sub>2</sub> and acetic acid in the absence of substrate, using low-temperature UV–Vis spectroscopy, suggests the in situ formation of a transient Fe(III)<sub>2</sub>-peroxido species. While the selectivity and nature of oxidation products implicate a high-valent iron-oxido complex as a key intermediate, the low alcohol/ketone ratios suggest a simultaneous radical-based process.</p>}},
  author       = {{Das, Biswanath and Al-Hunaiti, Afnan and Carey, Akina and Lidin, Sven and Demeshko, Serhiy and Repo, Timo and Nordlander, Ebbe}},
  issn         = {{0162-0134}},
  keywords     = {{Catalysis; Epoxidation; Hydroxylation; Iron; Metal-oxido complex; Peroxide complex}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Journal of Inorganic Biochemistry}},
  title        = {{A di‑iron(III) μ-oxido complex as catalyst precursor in the oxidation of alkanes and alkenes}},
  url          = {{http://dx.doi.org/10.1016/j.jinorgbio.2022.111769}},
  doi          = {{10.1016/j.jinorgbio.2022.111769}},
  volume       = {{231}},
  year         = {{2022}},
}